Method and system for supplying high purity fluid

ABSTRACT

A fluid purifying apparatus that includes a manifold that includes a first branch and a second branch, a first check valve coupled to the first branch of the manifold, and a purifier unit that includes a first end and a second end, wherein the first end is coupled to the second branch of the manifold. Also, a fluid purifying apparatus that includes a vessel that includes a first interior compartment for containing a purifier material and a second interior compartment for containment of a fluid containing impurities, wherein the first interior compartment is separated from the second interior compartment by a fluid permeable support, and a rupturable seal.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 10/331,123, filed Dec. 26, 2002, which is incorporated in itsentirety herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the field of fluid purification, and to thepurification of inert, non-reactive and reactive fluids. Furthermore,the invention relates to methods and materials for selectively removingtrace amounts of impurities from inert, non-reactive and reactivefluids.

2. Description of the Prior Art

The provision of high purity fluid streams is critically important in awide variety of industrial and research applications. The rapidexpansion of vapor-phase processing techniques, e.g., chemical vapordeposition, in the semiconductor industry has been associated with thedeployment and use of manufacturing equipment that is totally reliant onthe delivery of high purity process fluids at the point of use in thesemiconductor manufacturing facility.

Considering the impurities which are present in fluid streams involvedin semiconductor manufacturing, it is to be noted that the growth ofhigh quality thin film electronic and optoelectronic cells by chemicalvapor deposition or other vapor-based techniques is inhibited by avariety of low-level process impurities. These impurities can causedefects that reduce yields by increasing the number of rejects, whichcan be very expensive. These impurities may be particulate or chemicalcontaminants.

Chemical impurities may originate in the production of the source fluiditself, as well as in its subsequent packaging, shipment, storage, andhandling. Although source fluid manufacturers typically provide analysesof source gas materials delivered to the semiconductor manufacturingfacility, the purity of the fluids may change because of leakage into oroutgassing of the containers, e.g., gas cylinders, in which gases arepackaged. Impurity contamination may also result from improper fluidcontainers changes, leaks into downstream processing equipment, oroutgassing of such downstream equipment.

In semiconductor manufacturing processes, for example, removal ofimpurities helps to ensure the production of high-quality,high-performance semiconductor chips. Such impurities, when introducedonto the semiconductor chip during its manufacture, tend to render thechip deficient or even useless for its intended purpose. Thus, a growingnumber of industries are now requiring fluids having impurityconcentrations that do not exceed about 10 parts-per-billion (ppb)levels.

For example, in the manufacture of III-V semiconductor devices usingmetal-organic chemical vapor deposition (MOCVD), Group IIIAorganometallic source gases, such as tri-methyl aluminum, tri-methylindium and tri-methyl gallium may be purified by fractional distillationand/or sublimation to remove impurities. These organometallic compoundsare highly reactive with oxygen, and form oxygenated impurities that cansignificantly degrade the performance of III-V semiconductor devices.

There remains a need in the art for a reagent that removes contaminantssuch as oxygen and water from inert, non-reactive and reactive fluids.Further, there remains a need for purification methods and apparatusesthat provide relatively fast equilibration between fluid and purifier toensure adequate concentrations of purified fluid can be provided at thepoint of use. Also, a need exists for purifier materials that removeoxygen and oxygenated species and other impurities from inert,non-reactive and reactive fluids without concurrently emittingcontaminants such as moisture into the purified fluid stream.

SUMMARY OF THE INVENTION

One embodiment of the invention includes a fluid purifying apparatuscomprising a vessel comprising a first interior compartment forcontaining a purifier material and a second interior compartment forcontaining a fluid having impurities, wherein the first interiorcompartment is separated from the second interior compartment by a fluidpermeable support. In another embodiment, a membrane is provided betweenthe fluid and fluid permeable support, wherein the membrane prevents thefluid from contacting the purifier until the membrane is broken.

Another embodiment of the invention includes a fluid purifying apparatuscomprising a first container comprising a first fitting and a purifiermaterial, a second container comprising a second fitting and a fluid tobe purified, and a seal member interposed between the first fitting andthe second fitting when the first container is coupled to the secondcontainer, wherein the seal member comprises an inner membrane thatseparates the fluid to be purified from the purifier material until theinner membrane is broken.

Another embodiment of the invention includes a fluid purifying apparatuscomprising a manifold comprising a first branch and a second branch, afirst check valve coupled to the first branch of the manifold, and apurifier unit comprising a first end and a second end, wherein the firstend is coupled to the second branch of the manifold.

Another embodiment of the invention includes a fluid purifying apparatuscomprising a fluid vessel comprising a vessel valve, a purifier unitpositioned outside of said fluid vessel, wherein said purifier unitcomprises a first opening and a second opening, said first openingcoupled to the vessel valve and said second opening coupled to a pointof use for purified fluid, and a temperature control device thermallycoupled to the fluid vessel and the purifier unit.

Another embodiment of the invention includes a method of purifying afluid comprising providing a vessel comprising a first interiorcompartment and a second interior compartment, wherein the firstinterior compartment is separated from the second interior compartmentby a fluid permeable support; providing a purifier in the first interiorcompartment and a fluid in the second interior compartment; breaking amembrane that prevents the fluid from contacting the purifier; andpassing the fluid through the fluid permeable support and the purifierto remove impurities from the fluid.

Additional novel features shall be set forth in part in the descriptionthat follows, and in part will become apparent to those skilled in theart upon examination of the following specification or may be learned bythe practice of the invention. The features and advantages of theinvention may be realized and attained by means of theinstrumentalities, combinations, and methods particularly pointed out inthe appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a fluid storage and purification apparatus 100 according toone embodiment of the invention;

FIG. 2 shows a fluid storage and purification apparatus 200 according toanother embodiment of the invention;

FIG. 3 shows a fluid purification apparatus 300 according to anotherembodiment of the invention;

FIG. 4 shows a fluid purification apparatus 400 according to anotherembodiment of the invention;

FIG. 5 shows a fluid purification apparatus 500 according to anotherembodiment of the invention;

FIG. 6 shows a fluid purification apparatus 600 according to anotherembodiment of the invention;

FIG. 7 shows a fluid storage and purification apparatus 700 according toanother embodiment of the invention; and

FIG. 8 shows a purifier unit 800 according to another embodiment of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

The fluid purifying apparatus 100 of the invention is illustrated byFIG. 1 and comprises a branched manifold 104 that is positioned inside afluid storage vessel 101 and operatively engaged to a vessel valve 102that receives fluids F and dispenses purified fluids F′ from the vessel101. The individual elements of apparatus 100, such as the vessel 101,vessel valve 102, manifold 104, purifier unit 110, filter gaskets 108and 112, and check valves 106, 114 and 116 will be discussed in furtherdetail below. This branched manifold purifying apparatus 100 allows auser to introduce fluid F into storage vessel 101 through a branch ofmanifold 104 that terminates with check valve 116. The fluid Fintroduced to storage vessel 101 is then purified as it flows fromstorage vessel 101, through check valve 114, and into purifier unit 110where impurities are removed by purifier material P located withinpurifier unit 110. The purified fluid F′ is dispensed from vessel valve102 after exiting purifier unit 110 through check valve 106 that iscoupled to another branch of manifold 104.

Referring now to the details of apparatus 100 illustrated by FIG. 1, theapparatus 100 includes a manifold 104 positioned inside a fluid vessel101 and operatively engaged to a valve 102 that is coupled to the vessel101. Valve 102 is a conventional gas cylinder valve that has an outlet118 and a safety device 103. Safety device 103 is fitted with a metalburst disk (not shown) that ruptures when the pressure in the fluidvessel exceeds a safe level. The metal burst disk comprises a fusibleand/or meltable metal.

Manifold 104 has two branches: One branch terminates with a first checkvalve 116 that is biased to allow fluid F to flow from manifold 104 intovessel 101, but resists flow in the opposite direction (i.e., fromvessel 101 into manifold 104). The other branch of manifold 104 iscoupled to a second check valve 106, which in turn is coupled topurifier unit 110. Check valve 106 is biased to allow fluid F′ to flowfrom purifier unit 110 to manifold 104, but resists letting fluid F flowin the opposite direction (i.e., from manifold 104 to purifier unit110).

A filter gasket 108 is positioned between check valve 106 and purifierunit 110 to prevent particulate materials from clogging manifold 104 andvalve 102. Filter gasket 108 has an outer portion and an inner mesh: Theouter portion engages both check valve 106 and purifier unit 110 toleak-tightly couple these elements together, and the inner mesh trapspurifier material P and other particulates in purifier unit 110 whilepermitting fluid F′ to pass to check valve 106.

A third check valve 114 is coupled to purifier unit 110 opposite the endwhere check valve 106 couples to purifier unit 110. Check valve 114 hasthe same flow bias direction as check valve 106 and allows fluid F toflow from storage vessel 101 to purifier unit 110, but resists flow inthe opposite direction. Check valve 114 also keeps fluid F from flowinginto purifier unit 110 until valve 102 is opened.

Another filter gasket 112 is positioned between check valve 114 andpurifier unit 110 to prevent particulate materials from enteringpurifier unit 110 and also to hold the purifier materials P insidepurifier unit 110. Similar to filter gasket 108, filter gasket 112 hasan outer portion and an inner mesh: The outer portion engages bothpurifier unit 110 and check valve 114 to leak-tightly couple theseelements together. The inner mesh prevents particulate material in thefluid from entering purifier unit 110 and holds the purifier material Pinside the unit 110, while letting the fluid F pass into the unit 110.

Optionally, rupturable burst disks (not shown) leak-tightly sealpurifier unit 110 until a user is ready to dispense purified fluid F′ toa point of use. The burst disks have an outer ring portion that issealingly coupled to an end of purifier unit 110, and a rupturable innermembrane that leak-tightly seals that end of purifier unit 110 until themembrane is ruptured.

The fluid purifying apparatus 100 described above allows a user tointroduce fluid F that contains impurities through manifold 104 andcheck valve 116 and into vessel 101 where fluid F is stored untilneeded. When purified fluid F′ is needed, the user opens valve 102 andthe stored fluid F flows through check valve 114 and purifier unit 110where impurities are removed by purifier material P in purifier unit110.

When the pressure of fluid F alone is inadequate to force the fluid Fthrough the purifier unit 110, the user can add a carrier gas. The flowrate for fluid F (or fluid F and carrier gas) can range from about 0.001standard liters per minute (“splm”) to about 1000 splm, and can alsorange from about 1 splm to about 200 splm. If burst disks seal purifierunit 110, the pressure of fluid F (or a combination of fluid F and acarrier gas) ruptures the inner membrane of the disks to allow fluid Fto enter the purifier unit 110. The purified fluid F′ then exits thepurifier unit 110 and travels through check valve 106 and manifold 104before being dispensed to the point of use through an opening 118 invalve 102.

Fluid F includes liquids, gases, vapors, and multi-phase fluids (e.g.,single component fluids and mixtures). Examples of fluid F include,without being limited to, halogen containing compounds such as fluorine(F₂); chlorine (Cl₂); bromine (Br₂); iodine (I₂); hydrogen fluoride(HF); hydrogen chloride (HCl); hydrogen bromide (HBr); hydrogen iodide(HI); nitrogen trifluoride (NF₃); tungsten hexafluoride (WF₆); siliconhalide compounds such as dicholorosilane (SiH₂Cl₂), trichlorosilane(SiHCl₃), silicon tetrafluoride (SiF₄), silicon tetrachloride (SiCl₄);sulfur hexafluoride (SF₆); chlorine trifluoride (ClF₃); borontrichloride (BCl₃); boron trifluoride (BF₃); arsenic pentafluoride(AsF₅); germanium tetrafluoride (GeF₄); phosphorous trifluoride (PF₃);and halocarbons such as CF₄, NF₃, CHClF₂, CClF₂CF₃, CClF₃, CHCl₂F,CH₂F₂, and CH₃F, among other halogen containing compounds.

Examples of fluid F also include organic compounds such as saturated andunsaturated hydrocarbons including alkanes, alkenes and alkynes; cyclichydrocarbons including bicyclic and polycyclic ring compounds; aromatichydrocarbons including arenes and heteroarenes; oxygenated organiccompounds including alcohols, ethers, ketones, esters, and organicacids, among other oxygenated organic compounds; and nitrogen containingorganic compounds including amines, among other organic compounds.

Examples of fluid F further include hydrogen containing compounds, suchas hydrogen (H₂); ammonia (NH₃); silane (SiH₄); disilane (Si₂H₆); arsine(AsH₃); phosphine (PH₃); germane (GeH₄); diborane (B₂H₆); and SeH₂ amongother hydrogen containing compounds. Fluid F also includes, for example,oxygen containing compounds such as oxygen (O₂); carbon monoxide (CO);carbon dioxide (CO₂); nitrogen oxide (NO); nitrous oxide (N₂O); nitrogendioxide (NO₂); and carbonyl sulfide (COS), among other oxygen containingcompounds. Fluid F further includes, for example, inert compounds suchas nitrogen (N₂); helium (He); argon (Ar); neon (Ne); krypton (Kr);xenon (Xe); and radon (Rn), among other inert compounds.

Examples of fluid F also include, organometallic compounds comprising ametal and at least one organic group. Examples of the metal includealkali metals, alkali earth metals, transition metals such as GroupIIIA, IVA, VA, VIA, VIIA, VIII, Ib and IIb, and the Group IIIb, IVb, Vb,VIb metals (where the Group designation are defined by the ChemicalAbstracts Service periodic table group notation). The metal may alsoinclude polymetallic groups of two or more metals in the organometalliccompound. Examples of the organic group include linear, cyclic andaromatic hydrocarbons that are unsubstituted, and those that havesubstituted constituent groups such as alkyl hydrazines, arenes,heteroarenes, thiols, amines, alcohols, ethers, ketones, and carboxylicacids. Specific examples of organometallic compounds used with thepresent invention include alkyl amine-alanes, tri-alkyl aluminumcompounds, tri-alkyl gallium compounds, and tri-alkyl indium compounds,where the alkyl group comprises a methyl group, an ethyl group, a propylgroup, etc.

Sometimes a carrier gas is used in addition to fluid F to dilute theconcentration of fluid F and/or help fluid F flow through the purifyingapparatus and reach a point of use. Examples of carrier gas include,without being limited to, hydrogen (H₂) and inert gases such as nitrogen(N₂); helium (He); argon (Ar); neon (Ne); krypton (Kr); and xenon (Xe),among other carrier gases.

Purifying materials P that purify fluid F include substrates andsubstrates combined with metal compounds. The substrates may have avariety of forms such as beads, sheets, extrudates, powders and tablets,among other forms. The surface area of the substrate can have a rangefrom about 0.1 m²/g to about 1000 m²/g. Alternatively, the surface areacan have a range from about 1 m²/g to about 300 m²/g, or can have arange from about 10 m²/g to about 100 m²/g. The pore size of thesubstrate can be about 0.1 nm or larger in size. Alternatively, the poresize can be 2 nm or larger in size, or range from about 0.1 nm to about10 nm.

Examples of substrates used as purifying materials P include, withoutbeing limited to, metal oxides such as alumina (Al₂O₃); silica-alumina;silica (SiO₂); titania (TiO₂); zirconia (ZrO₂); and zeolites, amongother metal oxides. Examples also include carbon, graphite, and organicpolymers.

Metal compounds used in the purifying materials P can coversubstantially all the surface of the substrate. Alternatively, the metalcompounds can cover a range from about 5% to about 100% of the surface,or about 90% of the surface of the substrate. The metal compounds canact as the substrate itself, in which case the metal compound makes up100% of the surface of purifying material P. Examples of metal compoundsused in purifying materials P include, without being limited to, metalssuch as aluminum, magnesium, titanium, zinc, lithium, sodium, vanadium,chromium, molybdenum, tungsten, manganese, lead, bismuth, cobalt,tungsten, cerium, nickel, copper and iron, as well as alloys of themetals. Examples of the metal compounds also include oxides, nitrates,carbonates, oxalates, and hydrides of these metals.

As noted above, impurities are removed from fluid F by the fluidpurifying apparatus of the present invention. Examples of the impuritiesinclude, without being limited to, oxygen containing compounds such asoxygen containing organic and inorganic compounds, oxygen, water,hydroxides, peroxides, carbonates, carbon monoxide, carbon dioxide,ethers, alcohols, alkoxides, and alkyletherates adducts, among others.Examples of the impurities I also include sulfates, sulfites,thiosulfates, phosphates, nitrates, nitrites, halides, chalcides, andoxy-halides, among others.

When the impurities are removed from fluid F, the fluid F is consideredto be a “purified” fluid F′. It is to be understood that the terms“purified,” “pure” and “impure” are relative and not absolute terms. Forexample, commercially available argon having 500 ppb of impurities canhardly be considered heavily contaminated. Therefore, as used herein,“purified” fluids are those fluids that meet the purity specificationsfor a given process, and “impure” fluids are those fluids that do notmeet those purity specifications.

The concentrations of impurities in purified fluid F′ can include arange of from about 100 parts per billion (“ppb”) to about 0.01 ppb.Alternatively, the concentration can be about 10 ppb or less, 1 ppb orless, or 0.1 ppb or less.

Another embodiment of a fluid purifying apparatus 200 of the inventionis illustrated by FIG. 2 and comprises a branched manifold 204 that ispositioned inside a fluid storage vessel 201 and operatively engaged toa vessel valve 202 that receives fluids F and dispenses purified fluidsF′ from the vessel 201. In this embodiment, unions 208 and 212 are usedto couple the check valves 206 and 214 to the purifier unit 210.

Referring now to the details, the apparatus 200 includes a manifold 204positioned inside a fluid storage vessel 201 and operatively engaged toa valve 202 that is coupled to storage vessel 201. Manifold 204 has twobranches: One branch terminates with a first check valve 216 that isbiased to allow fluid F to flow from manifold 204 into storage vessel201, but resists flow in the opposite direction (i.e., from vessel 201into manifold 204). The other branch of manifold 204 is coupled to asecond check valve 206, which is biased to allow fluid F to flow frompurifier unit 210 to manifold 204, but resists letting fluid F flow inthe opposite direction (i.e., from manifold 204 to purifier unit 210).

A first union 208 is used to couple check valve 206 to purifier unit210. Union 208 comprises a first end and a second end opposite thefirst, where the first end sealingly engages check valve 206 and thesecond end sealingly engages purifier unit 210. A filter gasket 209 isaligned co-axially with and positioned approximately in the middle ofunion 208 to prevent particulate materials from clogging manifold 204and valve 202. Alternatively, the filter gasket can be positioned atapproximately the first or second end of the union 208. Filter gasket209 traps purifier material P and other particulates in the purifierunit 210 while permitting fluid F to pass to check valve 206.

A third check valve 214 is coupled to purifier unit 210 opposite the endwhere check valve 206 couples to purifier unit 210. Check valve 214 hasthe same flow bias direction as check valve 206 and allows fluid F toflow from the vessel 201 to the purifier unit 210, but resists flow inthe opposite direction. Check valve 214 also keeps fluid F from flowinginto purifier unit 210 until valve 202 is opened.

A second union 212 is used to couple check valve 214 to purifier unit210. Union 212 comprises a first end and a second end opposite thefirst, where the first end sealingly engages the purifier unit 210 andthe second end sealingly engages check valve 214. A filter gasket 213 isaligned co-axially with and positioned approximately in the middle ofunion 212. Alternatively, the filter gasket can be positioned atapproximately the first or second end of the union 212. The filtergasket 213 prevents particulate material in fluid F from enteringpurifier unit 210 and holds the purifier material P inside the unit 210,while letting fluid F pass into purifier unit 210.

Optionally, the unions 208 and 212 include rupturable burst disks (notshown) aligned co-axially with and coupled to the unions 208 and 212.The burst disks leak-tightly seal purifier unit 210 until a user isready to dispense purified fluid F′ to a point of use. The burst disksinclude a rupturable membrane that leak-tightly seals an end of purifierunit 210 until the membrane is ruptured.

Another embodiment of a fluid purifying apparatus 300 of the inventionis illustrated by FIG. 3 and comprises a chamber 304 that is positionedinside a fluid storage vessel 301 and operatively engaged to a vesselvalve 302 that receives fluids F and dispenses purified fluids F′ fromthe vessel 301. In this embodiment, a check valve 306 and a portion ofthe purifier unit 310 are positioned inside the chamber 304, which alsoincludes a port 318 that is coupled to another check valve 316. A userintroduces fluid F to storage vessel 301 by coupling a source of fluid Fto valve 302. When the user opens valve 302, fluid F will flood chamber304 and pass through port 318 and check valve 316 into storage vessel301. When the user is ready to dispense purified fluid F′ from thevessel 301, the fluid F stored in storage vessel 301 passes throughcheck valve 314 into purifier unit 310 where purifier material P removesimpurities from fluid F. Then, purified fluid F′ passes through checkvalve 306 into chamber 304 where it is dispensed through open valve 302to the point of use.

Filter gaskets 308 and 312 are aligned co-axially with and positioned atopposite ends of purifier unit 310. Similar to filter gaskets in otherembodiments of the invention, these filter gaskets 308 and 312 preventparticulate materials from entering purifier unit 310 and chamber 304while also holding purifier materials P inside purifier unit 310. Thepurifier apparatus 300 also optionally includes burst disks (not shown)that leak-tightly seal the purifier unit 310 until a user is ready todispense purified fluid F′ to a point of use.

Another embodiment of a fluid purifying apparatus 400 of the inventionis illustrated by FIG. 4 and comprises a branched manifold 404 that ispositioned inside a fluid storage vessel 401 and operatively engaged toa vessel valve 402 that receives fluids F and dispenses fluids F′ fromstorage vessel 401. In this embodiment, fluid F introduced to vessel 401travels through a port 418 aligned co-axially with purifier unit 410 andpasses through a check valve 416 that is positioned inside purifier unit410 before entering storage vessel 401. The walls of port 418 and checkvalve 416 are leak-tightly sealed to prevent fluid F from contacting thepurifier material P of the purifier unit 410. When a user is ready todispense purified fluid F′ from vessel 401, fluid F stored in the vessel401 passes through check valve 414 and into purifier unit 410 where thepurifier material P removes impurities from the fluid F. After theimpurities are removed, the purified fluid F′ passes through check valve406 into manifold 404 where it can be dispensed through open valve 402to a point of use.

Similar to other embodiments of the invention, the purificationapparatus 400 can include filter gaskets (not shown) to preventparticulate materials from entering purifier unit 410 and chamber 404while also holding purifier materials P inside the purifier unit 410.Likewise, the purifier apparatus 400 also optionally includes burstdisks (not shown) that leak-tightly seal purifier unit 410 until a useris ready to dispense purified fluid F′ to a point of use.

Another embodiment of a fluid purifying apparatus 500 of the inventionis illustrated by FIG. 5 and comprises a first container 502 operativelyengaged with a second container 504, where both containers 502 and 504are positioned inside a storage vessel 501. In this embodiment, fluid Fand purifier material P are stored separately from each other in storagevessel 501 until a user is ready to deliver purified fluid F′ to a pointof use.

The first container 502 contains a purifier material P and the secondcontainer 504 contains a fluid F. First container 502 also has a firstfitting 518 that is coupled to a second fitting 519 on second container504. The fittings 518 and 519 can be, for example, VCR type fittings orthreaded fittings that threadably engage the containers 502 and 504 in aleak-tight coupling.

A seal member 520 is co-axially aligned with and positioned between thefittings 518 and 519. Seal member 520 includes an outer ring portion 521that engages the sealing faces of the first and second fittings 518 and519 to form a leak-tight seal. The outer ring portion 521 can be madefrom a malleable metal or metal alloy. Alternatively, the outer ringportion 521 comprises an organic polymer such as plastic or rubber.

Seal member 520 also includes a rupturable inner membrane 522 to preventfluid F from contacting purifier material P until the inner membrane 522is ruptured. Seal member 520 is sealably engaged between first andsecond fitting 518 and 519 and fluid F is kept separate from purifiermaterial P by the unruptured inner membrane 522. When a user is ready tocontact fluid F with the purifier material P, the first container 502can be pressurized until the inner membrane 522 ruptures. Alternatively,fluid F can rupture inner membrane 522 after the vessel valve 507 isopened, or the second container 504 can be pressurized through port 514to cause the inner membrane 522 to rupture. Once the inner membrane 522is ruptured, fluid F in second container 504 passes to first container502 where impurities are removed from the fluid F by purifier materialP, and the purified fluid F′ is dispensed through open valve 507.

First container 502 has a port 505 that is coupled to a port 506 ofstorage vessel 501. The port 505 and port 506 are reversibly andleak-tightly coupled. Alternatively, port 505 and port 506 are weldedtogether, or the port 505 is replaced by an opening in container 502that is leak-tightly coupled to port 506. A filter gasket (not shown)covers the end of port 505 to prevent purifier material P and otherparticulates from clogging valve 507 and other downstream components ofpurifying apparatus 500.

The downstream components operatively engaging valve 507 include fitting508 that leak-tightly couples valve 507 with fluid regulator 510.Optionally, valve 507 is also operatively engaged with shutoff valves(not shown), flow control devices (not shown), and filter and/orpurifier units (not shown) downstream from valve 507.

A user can provide fluid F and purifier materials P to storage vessel501 through valve 507 and/or port 514. The user can evacuate storagevessel 501 before adding fluid F and purifier materials P. The fluid Fand purifier materials P can be loaded separately into vessel 501, orsimultaneously introduced as a mixture.

Another embodiment of a purifying apparatus 600 according to the presentinvention is illustrated in FIG. 6 and comprises a storage vessel 601that has an interior divided into a first and second compartment 602 and603 by a fluid permeable support 605. The vessel 601 also has arupturable membrane 611 positioned between fluid F and fluid permeablesupport 605. Rupturable membrane 611 prevents fluid F from contactingfluid permeable support 605 until rupturable membrane 611 is ruptured.Rupturable membrane 611 is made from a metal or polymer, such as ahalogenated polymer like polytetrafluoroethylene (i.e., Teflon).Alternatively, rupturable membrane 611 is made from a metal foil, wherethe metal can include, without being limited to, gold, silver, nickel,aluminum, stainless steel, and alloys thereof.

The first compartment 602 holds the purifier materials P. Alternatively,purifier materials can be held in compartment 603 and fluid F held incompartment 602, or fluid F and/or purifier P can be held in both firstand second compartments 602 and 603. A user introduces fluid F to thecompartment 603 of storage vessel 601 by opening shutoff valve 618 thatis coupled to conduit 620 that penetrates the fluid permeable support605 and membrane 611. Alternatively, a user can introduce fluid F to thecompartment 603 through port 614, or to compartment 602 through valve607.

When the user is ready to supply fluid F stored in storage vessel 601 toa point of use, valve 607 is opened. Fluid F passes through fluidpermeable support 605 and comes into contact with purifier material Pthat removes impurities from the fluid F. After the impurities areremoved, the purified fluid F′ passes through port 606, valve 607 andany other downstream components before reaching its point of use.Optionally, a filter gasket (not shown) covers the vessel-side openingof port 606 to prevent particulates and purifier materials from cloggingvalve 607 and other downstream components.

Another embodiment of a purifying apparatus 700 according to the presentinvention is illustrated in FIG. 7 and comprises a storage vessel 701operatively engaged with a purifying unit 710. In this embodiment,purifier unit 710 is positioned outside storage vessel 701 and at leastone temperature control device 703 is coupled to purifier unit 710and/or vessel 701.

A user introduces fluid F to apparatus 700 by loading fluid F throughport 706 that is coupled to vessel 701. Alternatively, a user canintroduce fluid F to storage vessel 701 through valve 702. When a useris ready to dispense purified fluid F to a point of use, valve 702 isopened and fluid F passes through valve 702 and conduit 704 beforeentering the purifier unit 710 where purifier material P removes theimpurities from fluid F. After the impurities are removed, the purifiedfluid F′ passes through conduit 711 and onto the point of use. Aregulator 712 is coupled to conduit 711 to regulate the pressure offluid F reaching the point of use. Filter gaskets (not shown) can becoupled to the ends of purifier unit 710 to prevent particulatematerials from entering purifier unit 710 and conduit 711 while alsoholding purifier materials P inside the unit 710.

The temperature of storage vessel 701 and purifier unit 710 arecontrolled during the operation of apparatus 700 by a temperaturecontrol device 703. Examples of the temperature control device 703include, without being limited to, heating tape, heating plates, heatingcoils, heating pads, heated or refrigerated cabinets, and baths oftemperature controlled fluids, among others.

Two or more, independently controllable temperature control devices canbe coupled to apparatus 700 that independently control the temperatureof different components of the apparatus 700. For example, onetemperature control device can be coupled to storage vessel 701 whileanother temperature control device is coupled to purifier unit 710. Inthis configuration, storage vessel 701 and purifier unit 710 can operateat different temperatures as fluid F′ is dispensed to a point of use.

Another embodiment of the invention is focused on a purifier unit 800that is illustrated by FIG. 8. The purifier unit 800, which is coupledexternally to a fluid vessel, comprises a container 810 coupled to amanifold 804 that is itself coupled to two unions 806 and 814. Fluid Ffrom a source coupled to union 806 passes through union 806 and port 816into container 810 that holds purifier material P. Impurities in fluid Fare removed by purifier material P and purified fluid F′ flows throughport 818 and union 814 towards a point of use.

Burst disks 808 and 812 are positioned between the first and secondunion 806 and 814 and their respective openings in manifold 804. Burstdisks 808 and 812 leak-tightly seal container 810, and prevent fluid Ffrom contacting purifier material P until burst disk 808 is ruptured.Burst disks 808 and 812 include an outer ring portion and a rupturableinner membrane: The outer ring portion engages the sealing faces ofunions 806 and 814 and manifold 804. Alternatively, burst disks 808 and812 can be coupled to the unions 806 and 814 by, for example, adhesives,welding, electroplating, or mechanical friction fitting, among othertechniques. The outer ring can be made from a metal or an organicpolymer, among other materials, as can the rupturable inner membrane.

Filter gaskets can be positioned between unions 806 and 814 and manifold804 to prevent particulate materials from entering container 810 whilealso holding purifier materials P inside the container 810.

Other embodiments of purifier unit 800 are contemplated where manifold804 has male openings (not shown) that can couple to female unions (notshown). In another embodiment, burst gaskets may be sealingly insertedinside the unions.

The present invention also includes methods of purifying a fluid F. Onemethod of removing an impurity from a fluid F comprises mixing the fluidF with a carrier gas in the interior compartment of a vessel, passingthe mixture of fluid F and carrier gas through a purifier unit insidethe vessel to purify the mixture and dispensing the purified mixture toa point of use.

Another method of purifying a fluid F containing impurities comprisesstoring fluid F in a vessel comprising an interior compartment and apurifier material P contained therein, wherein purifier material Pcomprises a metal compound formed on a substrate. The method alsocomprises flowing a carrier gas through the interior compartment of thevessel and dispensing a mixture of carrier gas and purified fluid F to apoint of use. In addition, the method comprises evacuating a portcoupled to a point of use and the vessel, and passing purified fluid F′from the vessel to the port.

In another method, a vessel is prepared to accept purifier materials Pby removing substantially all impurities from an interior compartment ofthe vessel and then supplying the vessel with purifier materials Pthrough a port coupled to the vessel. The port can be the same port usedto dispense the purified fluid F′. After purifier material P is suppliedto the port, a fluid F is added to the vessel. Alternatively, fluid Fand purifier materials P may be added simultaneously to the vessel as amixture.

Another method includes dispensing a purified fluid F′ from an apparatuscomprising: Providing a vessel with an interior compartment thatcomprises a purifier material P, wherein purifier material P comprises ametal deposited onto a substrate; and flowing a carrier gas through thevessel to remove purified fluid F′ from the purifier and dispensing fromthe vessel a mixture of purified fluid F′ and carrier gas, wherein thepurified fluid F′ dispensed from the vessel has impurity concentrationsof about 100 parts per billion (ppb) or less.

Still another method of removing an impurity from a fluid F comprisesproviding a vessel comprising a first interior compartment and a secondinterior compartment, wherein the first interior compartment isseparated from the second interior compartment by a fluid permeablesupport, providing a purifier material P in the first interiorcompartment and a fluid F in the second interior compartment, andpassing fluid F through the fluid permeable support and purifyingmaterial P to remove impurities from the fluid F.

The foregoing description is considered as illustrative only of theprinciples of the invention. The words “comprise,” “comprising,”“include,” “including,” and “includes” when used in this specificationand in the following claims are intended to specify the presence of oneor more stated features, integers, components, or steps, but they do notpreclude the presence or addition of one or more other features,integers, components, steps, or groups thereof. Furthermore, since anumber of modifications and changes will readily occur to those skilledin the art, it is not desired to limit the invention to the exactconstruction and process shown described above. Accordingly, allsuitable modifications and equivalents may be resorted to falling withinthe scope of the invention as defined by the claims that follow.

1. A fluid purifying apparatus comprising: a vessel comprising a firstinterior compartment and a second interior compartment, wherein thefirst interior compartment is separated from the second interiorcompartment by a fluid permeable support wherein said first interiorcompartment is capable of containing a purifier material and said secondinterior compartment is capable of containing a fluid containingimpurities.
 2. The apparatus of claim 1, wherein said purifier materialcomprises a metal compound deposited thereon.
 3. The apparatus of claim2, wherein said metal compound comprises reduced valent metal comprisingaluminum, magnesium, titanium, zirconium, vanadium, chromium,molybdenum, tungsten, manganese, zinc, lithium, sodium, lead, bismuth,cobalt, cerium, nickel, copper or iron.
 4. The apparatus of claim 2,wherein the metal compound comprises a metal hydride comprisingaluminum, magnesium, titanium, zirconium, vanadium, chromium,molybdenum, tungsten, manganese, zinc, lithium, sodium, lead, bismuth,cobalt, cerium, nickel, copper or iron.
 5. The apparatus of claim 1,wherein said purifier material comprises alumina, silicon oxide,zeolite, aluminosilicate, zirconium oxide, carbon, polymersor titaniumoxide.
 6. The apparatus of claim 1, wherein a surface area for saidpurifier material from about 0.1 m²/g to about 1000 m²/g.
 7. Theapparatus of claim 1, wherein a surface area for said purifier materialis from about 10 m²I/g to about 100 m²/g.
 8. The apparatus of claim 2,wherein a pore size for said purifier material is equal to or greaterthan about 0.1 nm.
 9. The apparatus of claim 1, wherein a pore size forsaid purifier material is equal to or greater than about 2 nm.
 10. Theapparatus of claim 1, wherein the fluid comprises an organometalliccompound.
 11. The apparatus of claim 10, wherein the organometalliccompound comprises a group IIa, IIb, IIIb, IVb, Vb, or VIb metal. 12.The apparatus of claim 11, wherein said group Ia, IIb, IIIb, IVb, Vb,and VIb metal comprises aluminum, gallium, germanium, tin, phosphorous,nitrogen, arsenic, antimony, sulfur, selenium, tellurium, magnesium,zinc or indium.
 13. The apparatus of claim 10, wherein theorganometallic compound comprises alkyl amine-alanes, metal alkylhydrazines, and tertiary butyl phosphine, tri-methyl gallium, tri-methylaluminum, or trimethyl indium.
 14. The apparatus of claim 1, whereinsaid impurities comprise an oxygenated compound.
 15. The apparatus ofclaim 1, wherein said impurities comprise molecular oxygen, water,carbon monoxide, carbon dioxide, ethers, alcohols, alkoxides, metals,hydrides, metal hydrides, metal carbonyls, metal halides, hydrocarbons,organometallic oxides, or alkyletherate adducts.
 16. The apparatus ofclaim 1, comprising a carrier gas to transport the fluid out of thevessel.
 17. The apparatus of claim 16, wherein said carrier gascomprises hydrogen, helium, argon or nitrogen.
 18. The apparatus ofclaim 1, wherein the fluid permeable support comprises a ceramic frit, aperforated metal disc, or a porous polymer.
 19. A fluid purifying vesselcomprising: a first interior compartment; and a second interiorcompartment, wherein the first interior compartment is separated fromthe second interior compartment by a fluid permeable support whereinsaid first interior compartment is capable of containing a purifiermaterial and said second interior compartment is capable of containing afluid containing impurities, wherein a surface area for said purifiermaterial from about 0.1 m²/g to about 1000 m²/g, wherein a pore size forsaid purifier material is equal to or greater than about 0.1 nm, andwherein the fluid comprises an organometallic compound.
 20. A fluidpurifying vessel comprising: a first interior compartment; and a secondinterior compartment, wherein the first interior compartment isseparated from the second interior compartment by a fluid permeablesupport wherein said first interior compartment is capable of containinga purifier material and said second interior compartment is capable ofcontaining a fluid containing impurities, wherein the fluid permeablesupport comprises a ceramic frit, a perforated metal disc, or a porouspolymer.